Agents for repelling insects and mites

ABSTRACT

Repelling insects and mites with acylated α,ω, aminoalcohol derivatives of the formula ##STR1## in which X represents hydrogen, COR 11 , COOR 12  or R 13 , 
     R 1  represents optionally subsituted alkyl or alkenyl radicals, 
     R 2 , R 11 , R 12  and R 13  are identical or different and represent optionally substituted alkyl or alkenyl radicals, 
     R 3  to R 10  are identical or different and represent hydrogen, or represent optionally substituted alkyl radicals, 
     and wherein 
     R 2  and R 3 , together with the atoms to which they are bonded, can also form an optionally subsituted monocyclic ring, and 
     n and m are identical or different and denote 0 or 1, 
     with the proviso that X does not represent hydrogen or R 13  if n and m represent 0. 
     Those compounds wherein R 2  and R 3  together are --(CH 2 ) 4  -- and R 1  is C 2  -C 6  -alkyl or C 3  -C 6  -alkenyl are new.

This is a division of application Ser. No. 165,684, filed Mar. 9, 1988,now U.S. Pat. No. 4,873,252.

The present invention relates to the use of acylated α,ω-aminoalcoholderivatives, some of which are known, as insect- and mite-repellentagents.

Agents which repel insects and mites (repellents) have the task ofpreventing harmful or troublesome arthrapods from coming into contactwith and from stinging and sucking or biting surfaces which attractthem, for example the skin of animals and humans, if these have notfirst been treated with such agents.

Numerous active compounds have already been proposed as repellents.(Compare, for example, K.H. Buuchel in Chemie der Pflanzenschutz- undSchadlingsbekampfungsmittel (Chemistry of the Plant Protection Agentsand Agents for combating Pests); published by: R. Wegler, Volume 1,Springer Verlag Berlin, Heidelberg, New York, 1970 page 487 et seq.).

3-Methyl-benzoic acid diethylamide (DEET), dimethyl phthalate and2-ethyl-hexane-1,3-diol are known in particular and have been used for arelatively long time, and of these above all DEET has achievedconsiderable importance in practice (see, for example, R. K. Kocher, R.S. Dixit, C. I. Somaya; Indian J. Med. Res. 62, 1 (1974)):

A considerable disadvantage of the known repellents is that theirpersistent action in some cases lasts only a relatively short time (onlya few hours).

Some of the compounds defined by the following formula (I) are known.

Corresponding polyhydroxyamines are known, for example, from ChemicalAbstracts 83 (25): 205/791.

N-Alkanoyl- and alkenoyl-hydroxyalkylpiperidines are furthermore knownfrom U.S. Patent No. 3,178,439. Other piperidines are known fromTetrahedron Suppl. 8/ Part 1 (1966) pages 113-121.

However, nothing has as yet been disclosed of an insect- andmite-repellent action of these compounds.

It has now been found that the acylated α,ω-aminoalcohol derivatives,some of which are known, of the formula I ##STR2## in which

X represents hydrogen, COR¹¹, COOR¹² or R¹³,

R¹ represents optionally substituted alkyl or alkenyl radicals,

R², R¹¹, R¹² and R¹³ are identical or different and represent optionallysubstituted alkyl or alkenyl radicals,

R³ to R¹⁰ are identical or different and represent hydrogen, orrepresent optionally substituted alkyl radicals,

and wherein

R² and R³, together with the atoms to which they are bonded, can alsoform an optionally substituted monocyclic ring, and

n and m are identical or different and denote 0 or 1,

with the proviso that X does not represent hydrogen or R¹³ if n and mrepresent 0,

have a potent insect- and mite-repellant action.

The repellent action is considerably better than that of the repellentsknown from the prior art. The active compounds according to theinvention thus represent a useful enrichment of the art.

The present invention thus relates to the use of acylatedα,ω-aminoalcohol derivatives of the general formula I for repellinginsects and mites.

The invention furthermore relates to insect- and mite-repellent agentswhich are characterized in that they contain at least one acylatedα,ω-aminoalcohol derivative of the general formula I.

The agents according to the invention containing at least one derivativeof the formula I can also contain other insect repellents. Virtually allthe customary repellent are possible here (compare, for example, K. H.Buchel in Chemie der Pflanzenschutz- und Schadlingsbekampfungsmittel(Chemistry of the Plant Protection Agents and Agents for CombatingPests); published by: R. Wegler, Volume 1, Springer Verlag Berlin,Heidelberg, New York, 1970, page 487 et seq.).

In the case of repellent combinations, the acylated α,ω-aminoalcohols ofthe general formula I are preferably used together with repellentcarboxylic acid amides, 1,3-alkanediols and carboxylic acid esters.Compounds which may be mentioned specifically are 3-methylbenzoic aciddiethylamide (DEET), 2-ethyl-hexane-1,3-diol (Rutgers 612) and dimethylphthalate.

The acylated α,ω-aminoalcohol derivatives which can be used according tothe invention are characterized by the general formula (I).

The radicals given in formula (I) preferably have the following meaning:

The alkyl group in the radicals R¹ to R¹³ is straight-chain or branchedand contains 1 to 12, preferably 1 to 8 and in particular 1 to 6, carbonatoms Examples which may be mentioned are methyl, ethyl, n- andi-propyl, n-, i- and t-butyl, n-pentyl and n-hexyl.

Optionally substituted alkenyl is straight-chain or branched alkenylwith preferably 2 to 10, in particular 2 to 7, carbon atoms. Exampleswhich may be mentioned are optionally substituted ethenyl, propen-1-yl,propen-2-yl, buten-1-yl, buten-2-yl and buten-3-yl.

The radicals R² and R³, together with the atoms they are bonded, canform 5-to 7-membered saturated rings, which can be substituted by 1 or2, preferably one, alkyl group, in particular methyl. The optionallysubstituted radicals R¹ to R¹³ can carry one or more, preferably 1 to 3and in particular 1 or 2, identical or different substituents.Substituents which may be mentioned are: alkyl with preferably 1 to 10,in particular 1 to 6, carbon atoms, such as methyl, ethyl, n- andi-propyl, n-, i.- and t-butyl, cyclopropyl, and cyclohexyl. Otherpossible substituents for R¹ to R¹³ are, for example, C₁ -C₄ -alkoxy,halogen and CN. Preferably, in the compounds of the general formula (I),one of the indices n and m represents 0 and the other represents 0 or 1,with the proviso that X does not represent hydrogen or R¹³ if n and mrepresent 0.

Compounds of the general formula (I) which are preferably used asrepellents are those in which

X represents hydrogen, COR¹¹ or R¹³,

R¹ represents C₁ -C₇ -alkyl or C₃ -C₇ -alkenyl,

R², R¹¹ and R¹³ are identical or different and represent C₁ -C₆ -alkyl,

R³ -R⁸ are identical or different and represent hydrogen or C₁ -C₆-alkyl,

wherein

R² and R³, together with the atoms to which they are bonded, can alsoform a 5- or 6-membered monocyclic ring, and

n represents 1 and

m represents 0.

Compounds of the general formula (I) which are particularly preferablyused as repellents are those in which

X represents hydrogen or R¹³, wherein

R¹³ represents C₁ -C₆ -alkyl,

R¹ represents C₁ -C₇ -alkyl or C₃ -C₇ -alkenyl,

R₄ to R₈ are identical or different and represent hydrogen or C₁ -C₆-alkyl,

R² and R³, together with the atoms to which they are bonded, form a 5-or 6-membered monocyclic ring,

n represents 1 and

m represents 0.

Compounds in which R¹ represents C₁ -C₇ -alkyl C₃ -C₇ -alkenyl, Xrepresents COR¹¹ or R¹³, R² and or R¹¹ are identical or different andrepresent C₁ -C₆ -alkyl, R³ to R⁸ are identical or different andrepresent hydrogen or C1-C6-alkyl, R13 represents C₁ -C₆ -alkyl, nrepresents 1 and m represents 0 are furthermore preferred.

Compounds of the general formula (I) which are especially preferred asrepellents are those in which m=0 and n=1, R¹ represents C₁ -C₄ -alkyl,R², R¹¹ and R¹³ are identical or different and represent C₁ -C₆ -alkyl,R³ to R⁸ represent hydrogen and X represents hydrogen, COR¹¹ or R¹³,wherein R¹¹ and R¹³ have the abovementioned meaning.

Compounds of the general formula (I) which are furthermore especiallypreferably used as repellents are those in which m=0 and n=1, R¹represents C₃ -C₄ alkyl, R² and R³, together with the atoms to whichthey are bonded, form a 6-membered ring, R⁴ to R⁸ represents hydrogenand X represents hydrogen or R¹³, wherein R¹³ represents C₁ -C₄ -alkyl.

The compounds of the general formula (I) are either known or can beprepared by known methods and processes (compare, for example, CesareFerri, Reaktionen der organischen Synthese (Reactions of organicsynthesis), Georg Thieme Verlag Stuttgart, 1978, page 223 and page 450).

The compounds of the formula (I) are accordingly obtained by a processin which the α,ω-aminoalcohols, which are known per se or can beprepared by known processes (compare, for example, Cesare Ferri,Reaktionen der org. Synthese (Reactions of organic synthesis), GeorgThieme Verlag Stuttgart, 1978, pages 211 et seq. and 496-497), of theformula (II) (II) ##STR3## wherein

R² to R¹⁰, n and m have the meaning given under formula (I)

are first reacted with carboxylic acid chlorides which are known per se,of the formula (III) ##STR4## wherein

R¹ has the meaning given under formula (I), if appropriate in thepresence of an acid acceptor, such as, for example, triethylamine orpotassium carbonate, and if appropriate using a diluent, such as, forexample, toluene, CH₂ Cl₂, tetrahydrofuran or acetonitrile, attemperatures between -40° and 110° C.

To prepare compounds of the general formula (I) in which X is other thanhydrogen, further acylation/alkylation is then carried out in a secondreaction step, if appropriate after isolation of the intermediateproduct with the free OH group, with carboxylic acid chlorides which areknown per se, of the formula (IV)

    R.sup.11 COCl                                              (IV)

to prepare compounds of the formula (I) where X=COR¹¹ ; chlorocarbonicacid esters of the formula (V) ##STR5## to prepare compounds of theformula (I) where X=COOR¹² ; or alkyl halides of the formula (VI)

    R.sup.13 --Y                                               (VI)

to prepare compounds of the formula (I) where X =R¹³ ; wherein, in theformula (IV), (V) and (VI), Y represents chlorine, bromine or iodine,preferably bromine or iodine, and R¹¹ to R¹³ have the abovementionedmeaning, if appropriate in the presence of an acid acceptor, such as,for example, triethylamine or potassium carbonate, or a base, such as,for example, sodium hydride, if appropriate using a diluent, such as,for example, toluene, tetrahydrofuran or acetonitrile, at temperaturesbetween 0° and 110° C. Working up is carried out by customary methods,for example by diluting the reaction mixture with water, extracting theproducts with methylene chloride or toluene and washing the organicphase with water, drying it and distilling it, or by so-called"incipient distillation", that is to say by prolonged heating tomoderately elevated temperatures under reduced pressure, in order tofree the products from the last volatile constituents.

Further purification can be carried out by chromatography on silica gelwith, for example, hexane:acetone=7:3 as the mobile phase.

The refractive index, melting point, Rf value or boiling point are usedto characterize the compounds.

The present invention also relates to new acylated α,ω-aminoalcoholderivatives of the formula ##STR6## wherein

R^(I) represents hydrogen, COR¹¹, COOR¹² or R¹³,

wherein

R¹¹, R¹² and R¹³ are identical or different and represent optionallysubstituted alkyl or alkenyl radicals and

R^(II) represents C₂ -C₆ -alkyl, or represents C₃ -C₆ -alkenyl

Preferred Compounds of general formula (Ia) are such

wherein

R^(I) represents hydrogen or R¹³

wherein

R¹³ stands for an optionally substituted alkyl or alkenyl radical and

R^(II) represents C₂ -C₆ -alkyl, or represents C₃ -C₆ -alkenyl.

The acylated α,ω-aminoalcohol derivatives of the formula ##STR7##wherein

R^(I) represents hydrogen, COR¹¹, COOR¹² or R¹³,

wherein

R¹¹, R¹² and R¹³ are identical or different and represent optionallysubstituted alkyl or alkenyl radicals and

R^(II) represents C₂ -C₆ -alkyl, or represents C₃ -C₆ -alkenyl,

are obtained by a process in which the α,ω-aminoalcohol of the formula##STR8## is reacted with a carboxylic acid chloride of the formula##STR9## wherein

R^(II) has the abovementioned meaning, if appropriate in the presence ofan acid acceptor, such as, for example, triethylamine or potassiumcarbonate, and if appropriate using an organic diluent, such as, forexample, toluene, methylene chloride, tetrahydrofuran or acetonitrile,at temperatures between -40° and 110° C., if appropriate the compoundsof the formula ##STR10## are isolated, and, if appropriate, the furtheracylation/alkylation is effected in a second reaction step withcarboxylic acid halides which are known per se (in particular carboxylicacid chlorides), of the formula

    R.sup.11 COCL                                              (IV)

to give compounds of the formula Ia where R^(I) =COR¹¹, or withchlorocarbonic acid esters of the formula ##STR11## to give compounds ofthe formula Ia where R^(I) =COOR¹², or with alkyl halides of the formula

    R.sup.13 --Y                                               (VI)

to give compounds of the formula Ia where R^(I) =R¹³, wherein

R¹¹, R¹² and R¹³ have the abovementioned meaning and

Y represents chlorine, bromine or iodine, preferably bromine or iodine,

if appropriate in the presence of an acid acceptor, such as, forexample, triethylamine or potassium carbonate, or a base, such as sodiumhydride, if appropriate using an organic diluent, such as, for example,toluene, tetra-hydrofuran or acetonitrile, preferably at temperaturesbetween 0° and 110° C.

The compounds of the formula (Ia) according to the invention are workedup in a manner analogous to that described above for the preparation ofthe compounds of the formula (I).

The action of the repellents of the general formula (I) persists for along time.

They can therefore be used with good success for repelling harmful ortroublesome sucking and biting insects and mites.

The sucking insects essentially include the mosquitoes (for exampleAedes, Culex and Anopheles species), owl gnats (Phlebotoma), blackfly(Culicoides species), buffalo gnats (Simulium species), biting flies(for example Stomoxys calcitrans), tsetse flies (Glossina species),horseflies (Tabanus, Haematopota and Chrysops species), houseflies (forexample Musca domestica and Fannia canicularis), meat flies (for exampleSarcophaga carnaria), flies which cause myiasis (for example Luciliacuprina, Chrysomyia chloropyga, Hypoderma bovis, Hypoderma lineatum,Dermatobia hominis, Oestrus ovis, Gasterophilus intestinalis andCochliomyia hominovorax), bugs (for example Cimex lectularius, Rhodniusprolixus and Triatoma infestans), lice (for example Pediculus humanus,Haematopinus suis and Damalina oris), louse flies (for exampleMelaphagus orinus), fleas (for example Pulex irritans, Cthenocephalidescanis and Xenopsylla cheopis) and sand fleas (for example Dermatophiluspenetrans).

The biting insects essentially include cockroaches (for example Blatellagermanica, Periplaneta americana, Blatta orientalis and Supellasupellectilium), beetles (for example Sitophilus granarius, Tenebriomolitor, Dermestes lardarius, Stegobium paniceum, Anobium puntactum andHylotrupes bajulus), termites (for example Reticulitermes lucifugus) andants (for example Lasius niger).

The mites include ticks (for example Ornithodorus moubata, Ixodesricinus, Boophilus microplus and Amblyomma hebreum) and mites in thenarrower sense (for example Sarcoptes scabiei and Dermanyssus gallinae).

The active compounds according to the invention, which can be usedundiluted or, preferably, in diluted form, can be converted into theformulations customary for repellents. They can in general be used inall the presentation forms customary in cosmetics, for example in theform of solutions, emulsions, gels, ointments, pastes, creams, powders,sticks, sprays or aerosols from spray cans.

For use in the non-cosmetic sector, the active compounds can beincorporated, for example, into granules, oil-based spraying agents orslow release formulations.

The formulations are prepared in a known manner by mixing or dilutingthe active compounds according to the invention with solvents (forexample xylene, chlorobenzenes, paraffins, methanol, ethanol,isopropanol or water), carriers (for example kaolins, aluminas, talc,chalk, highly disperse silicic acid and silicates), emulsifying agents(for example polyoxyethylene fatty acid esters, polyoxyethylene fattyalcohol ethers, alkylsulphonates and arylsulphonates) and dispersingagents (for example lignin, sulphite waste liquors and methylcellulose).

The active compounds according to the invention can be used in theformulations as mixtures with one another or as mixtures with otherknown active compounds (for example sunscreen agents) The formulationsin general contain between 0.1 and 95% by weight of active compound,preferably between 0.5 and 90%.

For protection from blood-sucking insects or mites, the active compoundsaccording to the invention are either applied to the human or animalskin, or items of clothing and other articles are treated with them.

The active compounds according to the invention are also suitable as anadditive to impregnating agents for, for example, textile webs, items ofclothing and packaging materials, and as an additive to polishing,cleaning and window-cleaning agents.

The following examples of formulations and the use of the activecompounds according to the invention serve for further illustration ofthe invention.

EXAMPLE 1

A repellent in the form of a lotion for use on the skin is prepared bymixing 30 parts of one of the active compounds according to theinvention, 1.5 parts of perfume and 68.5 parts of isopropanol. Theisopropanol can be replaced by ethanol.

EXAMPLE 2

A repellent in the form of an aerosol for spraying onto the skin isprepared by formulating 50% of an active compound solution consisting of30 parts of one of the active compounds according to the invention, 1.5parts of perfume and 68.5 parts of isopropanol with 50% of Frigen 11/12(=halogenated hydrocarbon as a propellant gas) as a spray can.

EXAMPLE 3

Another spray can consists of 40% of an active compound solutionconsisting of 20 parts of one of the active compounds according to theinvention, 1 part of perfume and 79 parts of isopropanol and 60% ofpropane/butane (ratio 15.85)

Individual formulations are prepared according to Examples 1, 2 and 3using the following active compounds: compounds according to PreparationExamples Nos. 1, 2, 3, 8 and 15.

The following examples of the biological action show the superiority ofthe substances according to the invention compared with the prior art(diethyltoluamide =DEET):

EXAMPLE A

Repellent test on guineapigs

Test insect: Aedes aegypti (imagines)

Number of test insects: about 5,000

Solvent: Ethanol (99.8%)

3 parts by weight of active compound are taken up in 100 parts by volumeof solvent.

A guineapig is shaved on its back over an area of 50 cm² and is fixed ina narrow cage (box) so that only the shaved area is accessible tomosquitoes. The area is treated with 0.4 ml of active compound solutionand, after the solvent has evaporated, the guineapig, together with thebox, is placed in a cage measuring 60×60×60 cm containing only the testinsects of both sexes fed with sugared water.

The number of mosquitoes which sting the guineapig is observed for 10minutes. The guineapig is then removed and the test is repeated againafter one hour. The experiment is carried out for a maximum of 14 hours,or until the action stops.

In this test, for example, the following compounds from the preparationexamples show a superior action compared with the prior art(diethyltoluamide=DEET): (1), (2), (3), (8), (15) and (28).

                  TABLE A                                                         ______________________________________                                        Repellent test on guineapigs                                                                          Number of                                                                     stings after:                                         Product                   0.sup.h -6.sup.h                                                                     7.sup.h -14.sup.h                            ______________________________________                                        According to the invention: Prep. Ex. No. 1                                            ##STR12##            0.1    6.3                                      Prep. Ex. No. 8                                                                        ##STR13##            1.9    3.6                                      Prep. Ex. No. 2                                                                        ##STR14##            0.1    0.6                                      Prep. Ex. No. 15                                                                       ##STR15##            0.3    1.6                                      Prep. Ex. No. 3                                                                        ##STR16##            0.1    3.5                                      Prep. Ex. No. 29                                                                       ##STR17##            0.1    2.4                                      Known: DEET                                                                            ##STR18##            2.4    11.6                                     ______________________________________                                         Note:                                                                         "Prep. Ex." denotes "Preparation Example"-                               

EXAMPLE B

Repellent test on guineapigs

Test insect: Culex pipiens fatigans

Number of test insects about 1,000

Solvent: Ethanol (99.8%)

3 parts by weight of active compound are taken up in 100 parts by volumeof solvent.

A guineapig is shaved on its back over an area of 50 cm² and is fixed ina narrow cage (box) so that only the shaved area is accessible tomosquitoes. The area is treated with 0.4 ml of active compound solutionand, after the solvent has evaporated, the guineapig, together with thebox, is placed in a cage measuring 60×60×60 cm containing only the testinsects of both sexes fed with sugared water.

The number of mosquitoes which sting the guineapig is observed for 10minutes.

The guineapig is then removed and the test is repeated again after onehour. The experiment is carried out for a maximum of 10 hours, or untilthe action stops.

In this test, for example, the following compounds from the preparationexamples show a superior action compared with the prior art(diethyltoluamide=DEET): (3), (8), (15), (29).

                  TABLE B                                                         ______________________________________                                        Repellent test on guineapigs                                                                          Number of                                                                     stings after:                                         Product                   0.sup.h -6.sup.h                                                                     7.sup.h -10.sup.h                            ______________________________________                                        According to the invention: Prep. Ex. No. 8                                            ##STR19##            0.1    3.1                                      Prep. Ex. No. 15                                                                       ##STR20##            0.1    2.2                                      Prep. Ex. No. 3                                                                        ##STR21##            0      0.6                                      Prep. Ex. No. 29                                                                       ##STR22##            0      0.2                                      Known:                                                                                 ##STR23##            0.1    4.9                                      ______________________________________                                         Note:                                                                         "Prep. Ex." denotes "Preparation Example"-                               

PREPARATION EXAMPLES PREPARATION EXAMPLES 1N,O-Bis-acetyl-N-butyl-1,3-aminopropanol

40 g (0.3 mol) of N-butyl-1,3-aminopropanol and 100 ml of triethylamine(0.72 mol) are dissolved in 1 liter of tetrahydrofuran, and 50 ml ofacetyl chloride (0.7 mol) are added at 20° C. The mixture is warmedunder reflux for one day and the solid is then filtered off. Methylenechloride is added and the organic layer is washed with water. Theorganic phase is then dr1ed with magnesium sulphate, the solvent isdistilled off on a rotary evaporator and the residue is distilled in abulb tube oven (boiling point 0.6 135°-140° C.). For furtherpurification, the substance is chromatographed over 1 kg of silica gel(mobile phase cyclohexane:acetone=7:3).

Yield: 52.1 g=81% of theory

PREPARATION EXAMPLE 2 1-Pentanoyl-2-(2-hydroxyethyl)-piperidine

65 g (0.5 mol) of 2-(2-hydroxyethyl)-piperidine and 90 ml oftriethylamine (0.64 mol) are dissolved in 1 liter of tetrahydrofuran,and 80 ml (0.67 mol) of valeryl chloride are added at -20° C. Themixture is warmed at 20° C. for one day and the solvent is then largelyremoved on a rotary evaporator; the residue is taken up in methylenechloride, the mixture is washed with 1N NaOH solution, the organic phaseis dried and the solvent is removed by distillation on a rotaryevaporator. In order to remove impurities of the bis-acylated compound,the product is taken up in 200 ml of ethanol and the mixture is warmedat 50° C. with 200 ml of 1N sodium hydroxide solution for one hour. Itis evaporated on a rotary evaporator again, the residue is extractedwith CH₂ Cl₂ /H₂ O, the organic phase is dried and evaporated on arotary evaporator and the residue is distilled in a bulb tube oven(boiling point₀.2 =165° C.).

Yield: 65.4=61% of theory.

PREPARATION EXAMPLE 3 1-Pentanoyl-2-(2-methoxethyl)-piperidine

32 g (0.15 mol) of 1-pentanoyl-2-(2-hydroxyethyl)-piperidine aredissolved in 300 ml of tetrahydrofuran, and 5.9 g (0.197 mol) of sodiumhydride (80% strength in paraffin) are added at 20° C. The mixture iswarmed under reflux for 4 hours and 20 ml of methyl iodide (0.32 mol)are then added to the reaction mixture.

The mixture is then warmed under reflux for 8 hours, 100 ml of ammoniumchloride solution are subsequently added at 20° C., the mixture isextracted with methylene chloride and the organic phase is dried withmagnesium sulphate and evaporated on a rotary evaporator Afterpurification by chromatography (mobile phase CH₂ Cl₂ :i-C₃ H₇ OH=1:1;silica gel), the product is evaporated on a rotary evaporator and theresidue is distilled in a bulb tube oven (boiling point₀.2 : 160° C.).

Yield: 27.7 g=81% of theory.

The further preparation examples listed in the table below weresynthesized analogously to the above Preparation Examples 1 to 3.

    __________________________________________________________________________     ##STR24##                                                   (I)              Prep.                                                 physical                Ex.                                                   data                    No. R.sup.1  R.sup.2     R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                         R.sup.6                                                                         R.sup.7                                                                         R.sup.8                                                                         R.sup.9                                                                         R.sup.10                                                                         n m X       (n.sub.D.sup.20)        __________________________________________________________________________     4  C.sub.2 H.sub.5                                                                        n-C.sub.4 H.sub.9                                                                         H H H H --                                                                              --                                                                              --                                                                              -- 0 0 COC.sub.2 H.sub.5                                                                     1.455                    5  CH.sub.3 n-C.sub.4 H.sub.9                                                                         H H H H --                                                                              --                                                                              --                                                                              -- 0 0 COCH.sub.3                                                                            1.457                    6  CH.sub.3 n-C.sub.4 H.sub.9                                                                         H H H H H H H H  1 1 COCH.sub.3                                                                            1.4565                   7  CH.sub.3 C.sub.2 H.sub.5                                                                           H H H H H H --                                                                              -- 1 0 COCH.sub.3                                                                            1.4532                   8  CH.sub.3 t-C.sub.4 H.sub.9                                                                         H H H H H H --                                                                              -- 1 0 COCH.sub.3                                                                            1.4565                   9  CH.sub.3 n-C.sub.3 H.sub.7                                                                         H H H H H H --                                                                              -- 1 0 COCH.sub.3                                                                            1.4540                  10  CH.sub.3 CH.sub.3    H H H H H H --                                                                              -- 1 0 COCH.sub.3                                                                            1.4530                  11  CH.sub.3 CH.sub.3    H H H H H H --                                                                              -- 1 0 H       1.4660                  12  n-C.sub.4 H.sub.9                                                                      (CH.sub.2).sub.4                                                                            H H H H H --                                                                              -- 1 0 COCH.sub.3                                                                            1.4770                  13  CH.sub.3 (CH.sub.2).sub.4                                                                            H H H H H --                                                                              -- 1 0 COCH.sub.3                                                                            1.4780                  14  CH.sub.3  i-C.sub.3 H.sub.7                                                                        H H H H H H --                                                                              -- 1 0 COCH.sub.3                                                                            1.4549                  15  n-C.sub.4 H.sub.9                                                                      CH.sub.3    H H H H H H --                                                                              -- 1 0 COC.sub.4 H.sub.9 -(n)                                                                1.4526                  16  n-C.sub.4 H.sub.9                                                                      (CH.sub.2).sub.4                                                                            H H H H H --                                                                              -- 1 0 COOC.sub.2 H.sub.5                                                                    1.4650                  17  n-C.sub.4 H.sub.9                                                                      n-C.sub.4 H.sub.9                                                                         H H H H H H --                                                                              -- 1 0 H       1.4655                  18  n-C.sub.5 H.sub.11                                                                     n-C.sub.4 H.sub.9                                                                         H H H H H H --                                                                              -- 1 0 H       1.4649                  19  C.sub.2 H.sub.5                                                                        (CH.sub.2).sub.4                                                                            H H H H H --                                                                              -- 1 0 H       1.4960                  20  CH.sub.3 (CH.sub.2).sub.4                                                                            H H H H H --                                                                              -- 1 0 H       1.4990                  21  n-C.sub.3 H.sub.7                                                                      (CH.sub.2).sub.4                                                                            H H H H H --                                                                              -- 1 0 H       1.4905                  22  n-C.sub.4 H.sub.9                                                                      CH.sub.3    H H H H H H --                                                                              -- 1 0 CH.sub.3                                                                              1.4510                  23  n-C.sub.5 H.sub.11                                                                     (CH.sub.2).sub.4                                                                            H H H H H --                                                                              -- 1 0 H       1.4995                  24  n-C.sub.4 H.sub.9                                                                      (CH.sub.2).sub.4                                                                            H H H H H --                                                                              -- 1 0 C.sub.2 H.sub.5                                                                       1.4730                  25  n-C.sub.4 H.sub.9                                                                      (CH.sub.2).sub.4                                                                            H H H H H --                                                                              -- 1 0 n-C.sub.3 H.sub.7                                                                     1.4711                  26  n-C.sub.4 H.sub.9                                                                      (CH.sub.2).sub.4                                                                            H H H H H --                                                                              -- 1 0 n-C.sub.4 H.sub.9                                                                     1.4713                  27  n-C.sub.4 H.sub.9                                                                      (CH.sub.2).sub.3                                                                            H H H H H --                                                                              -- 1 0 H       1.4854                  28  CH.sub.3                                                                                ##STR25##  H H H H H H --                                                                              -- 1 0 COCH.sub.3                                                                            1.4625                  29  t-C.sub.4 H.sub.9                                                                      (CH.sub.2).sub.4                                                                            H H H H H --                                                                              -- 1 0 H       1.4873                  30  CH(C.sub.2 H.sub.5)C.sub.4 H.sub.9                                                     (CH.sub.2).sub.4                                                                            H H H H H --                                                                              -- 1 0 H       1.4852                  31  CH.sub.3                                                                                ##STR26##  H H H H H H --                                                                              -- 1 0 COOC.sub.4 H.sub.9                                                                    1.4588                  32  CHCHC.sub.2 H.sub.5                                                                    (CH.sub.2).sub.4                                                                            H H H H H --                                                                              -- 1 0 H       1.5159                  33                                                                                 ##STR27##                                                                             (CH.sub.2).sub.4                                                                            H H H H H --                                                                              -- 1 0 H       1.5034                  34  CHCHCH.sub.3                                                                           (CH.sub.2).sub.4                                                                            H H H H H --                                                                              -- 1 0 H       1.5200                  35  t-C.sub.4 H.sub.9                                                                      (CH.sub.2).sub.4                                                                            H H H H H --                                                                              -- 1 0 H       (-)-Form:                                                                     [α].sub.365 =                                                           -127.1°                                                                (C = 1.5;THF)           36  t-C.sub.4 H.sub.9                                                                      (CH.sub.2).sub.4                                                                            H H H H H --                                                                              -- 1 0 H       (+)-Form:                                                                     [α].sub.365 =                                                           125.0°                                                                 (C = 1.5;THF)           37  t-C.sub.4 H.sub.9                                                                      (CH.sub.2).sub.4                                                                            H H H H H --                                                                              -- 1 0 COC.sub.4 H.sub.9 -t                                                                  1.4700 (n.sub.                                                                D.sub.20)               38  C(CH.sub.3).sub.2 C.sub.2 H.sub.5                                                      (CH.sub.2).sub.4                                                                            H H H H H --                                                                              -- 1 0 H       1.4906                                                                        (n.sub.20.sub.D)        39  C.sub.4 H.sub.9                                                                        (CH.sub.2).sub.3                                                                            H H H H H --                                                                              -- 0 0 COCH.sub.3                                                                            1.4747 (n.sub.                                                                D.sup.20)               40  CH.sub.3 CH.sub.2CHCHCH.sub.3                                                                      H H H H H H --                                                                              -- 1 0 COCH.sub.3                      41  CH.sub.3 CH.sub.2CHCHCH.sub.3                                                                      H H H H H H --                                                                              -- 1 0 H                               __________________________________________________________________________     THF = Tetrahydrofuran                                                    

What is claimed is:
 1. A method of repelling insects and mites which comprises applying to a locus from which it is desired to exclude such insects and mites an insect- and mite epellent effective amount of at least one acylated α,ω-amino-alcohol derivative of the formula ##STR28## wherein R¹ represents hydrogen, COR¹¹, COOR¹² or R¹³, wherein R¹¹, R¹² and R¹³ are identical or different and represent alkyl containing up to twelve carbon atoms or alkenyl containing up to ten carbon atoms and R¹¹ represents C₂ -C₆ -alkyl, or represents C₃ -C₆ -alkenyl.
 2. The method according to claim 1, in whichR¹ represents hydrogen or R¹³, wherein R¹³ stands for alkyl containing up to ten carbon atoms or alkenyl containing up to ten carbon atoms and R^(II) represents C₂ -C₆ -alkyl, or represents C₃ -C₆ -alkenyl hydrogen or C₁ -C₆ -alkyl,wherein R² and R³, together with the atoms to which they are bonded, can also form a 5- or 6-membered monocyclic ring, and n represents 1 and m represents
 0. 3. The method according to claim 1, wherein such compound is 1-pentanoyl-2-(2-hydroxyethyl)-piperidine of the following ##STR29##
 4. The method according to claim 1, wherein such compound is 1-(dimethylpropionyl)-2-(2-hydroxyethyl)-piperidine of the formula ##STR30## 